Spatiotemporal control of photochromic upconversion through interfacial energy transfer.

Dynamic control of multi-photon upconversion with rich and tunable emission colors is stimulating extensive interest in both fundamental research and frontier applications of lanthanide based materials. However, manipulating photochromic upconversion towards color-switchable emissions of a single lanthanide emitter is still challenging. Here, we report a conceptual model to realize the spatiotemporal control of upconversion dynamics and photochromic evolution of Er3+ through interfacial energy transfer (IET) in a core-shell nanostructure. The design of Yb sublattice sensitization interlayer, instead of regular Yb3+ doping, is able to raise the absorption capability of excitation energy and enhance the upconversion. We find that a nanoscale spatial manipulation of interfacial interactions between Er and Yb sublattices can further contribute to upconversion. Moreover, the red/green color-switchable upconversion of Er3+ is achieved through using the temporal modulation ways of non-steady-state excitation and time-gating technique. Our results allow for versatile designs and dynamic management of emission colors from luminescent materials and provide more chances for their frontier photonic applications such as optical anti-counterfeiting and speed monitoring.

Cross Relaxation Enables Spatiotemporal Color-Switchable Upconversion in a Single Sandwich Nanoparticle for Information Security.

Smart control of ionic interaction dynamics offers new possibilities for tuning and editing luminescence properties of lanthanide-based materials. However, it remains a daunting challenge to achieve the dynamic control of cross relaxation mediated photon upconversion, and in particular the involved intrinsic photophysics is still unclear. Herein, this work reports a conceptual model to realize the color-switchable upconversion of Tm3+ through spatiotemporal control of cross relaxation in the design of NaYF4:Gd@NaYbF4:Tm@NaYF4 sandwich nanostructure. It shows that cross relaxation plays a key role in modulating upconversion dynamics and tuning emission colors of Tm3+. Interestingly, it is found that there is a short temporal delay for the occurrence of cross relaxation in contrast to the spontaneous emission as a result of the slight energy mismatch between relevant energy levels. This further enables a fine emission color tuning upon non-steady state excitation. Moreover, a characteristic quenching time is proposed to describe the temporal evolution of cross relaxation quantitatively. These findings present a deep insight into the physics of ionic interactions in heavy doping systems, and also show great promise in frontier applications including information security, anti-counterfeiting and nanophotonics.

Selectively Manipulating Interactions between Lanthanide Sublattices in Nanostructure toward Orthogonal Upconversion.

Smart control of ionic interactions is a key factor to manipulate the luminescence dynamics of lanthanides and tune their emission colors. However, it remains challenging to gain a deep insight into the physics involving the interactions between heavily doped lanthanide ions and in particular between the lanthanide sublattices for luminescent materials. Here we report a conceptual model to selectively manipulate the spatial interactions between erbium and ytterbium sublattices by designing a multilayer core-shell nanostructure. The interfacial cross-relaxation is found to be a leading process to quench the green emission of Er3+, and red-to-green color-switchable upconversion is realized by fine manipulation of the interfacial energy transfer on the nanoscale. Moreover, the temporal control of up-transition dynamics can also lead to an observation of green emission due to its fast rise time. Our results demonstrate a new strategy to achieve orthogonal upconversion, showing great promise in frontier photonic applications.

Thermodynamics and Kinetics Accounting for Antithermal Quenching of Luminescence in Sc2(MoO4)3: Yb/Er: Perspective beyond Negative Thermal Expansion.

Defects are common in inorganic materials and not static upon annealing of the heat effect. Antithermal quenching of luminescence in phosphors may be ascribed to the migration of defects and/or ions, which has not been well-studied. Herein, we investigate the antithermal quenching mechanism of upconversion luminescence in Sc2(MoO4)3: 9%Yb1%Er with negative thermal expansion via a fresh perspective on thermodynamics and kinetics, concerning the thermally activated movement of defects and/or ions. Our results reveal a second-order phase transition taking place at ∼573 K induced by oxide-ion migration. The resulting variation of the thermodynamics and kinetics of the host lattice owing to the thermally induced oxide-ion movement contributes to a more suppressed nonradiative decay rate. The dynamic defects no longer act as quenching centers with regard to the time scale during which they stay nearby the Yb3+/Er3+ site in our proposed model. This research opens an avenue for understanding the antithermal quenching mechanism of luminescence via thermodynamics and kinetics.

Multichannel Control of PersL/Upconversion/Down-Shifting Luminescence in a Single Core-Shell Nanoparticle for Information Encryption.

Persistent luminescence (PersL) has been attracting substantial attention in diverse frontier applications such as optical information security and in vivo bioimaging. However, most of the reported PersL emissions are based on the dopants instead of the host matrix, which also plays an important role. In addition, there are few works on the PersL-based multifunctional nanoplatform in nanosized materials. Here, we report a class of novel nanostructure designs with PersL, upconversion, and down-shifting luminescence to realize the fine-tuning of emission colors under different excitation modes including steady-state irradiation, time-gating, and PersL generation. Blue, orange, and green emissions were easily achieved in such a single nanoparticle under suitable excitation modes. Moreover, the physical origin of the PersL of the CaF2 matrix was discussed by simulating the energy band structure with CaxFy defects. Our results provide new opportunities for the design of a new class of multifunctional materials, showing great promise in the field of information encryption security and multilevel anticounterfeiting.

Activating Ultrahigh Thermoresponsive Upconversion in an Erbium Sublattice for Nanothermometry and Information Security.

Thermal activation of upconversion luminescence in nanocrystals opens up new opportunities in biotechnology and nanophotonics. However, it remains a daunting challenge to achieve a smart control of luminescence behavior in the thermal field with remarkable enhancement and ultrahigh sensitivity. Moreover, the physical picture involved is also debatable. Here we report a novel mechanistic design to realize an ultrasensitive thermally activated upconversion in an erbium sublattice core-shell nanostructure. By enabling a thermosensitive property into the intermediate 4I11/2 level of Er3+ through an energy-migration-mediated surface interaction, the upconverted luminescence was markedly enhanced in the thermal field together with a striking thermochromic feature under 1530 nm irradiation. Importantly, the use of non thermally coupled red and green emissions contributes to the thermal sensitivity up to 5.27% K-1, 3 times higher than that obtained by using conventional thermally coupled green emissions. We further demonstrate that the controllable surface interaction is a general approach to the thermal enhancement of upconversion for a series of lanthanide-based nanomaterials. Our findings pave a new way for the development of smart luminescent materials toward emerging applications such as noncontact nanothermometry, information security, and anticounterfeiting.

Ultrasensitive Thermochromic Upconversion in Core-Shell-Shell Nanoparticles for Nanothermometry and Anticounterfeiting.

Upconversion nanoparticle based ratiometric nanothermometry has shown many advantages including high relative sensitivity, fast temperature response, and high spatial resolution. However, most of the existing designs are on the basis of thermally coupled upconversion emissions, and it remains a challenge to improve the thermo-sensitivity. Here, we report a new nanoplatform of NaYF4:Yb/Er/Ce@NaYF4@NaYF4:Yb/Tm core-shell-shell nanostructure to improve the thermal sensitivity through the nonthermally coupled upconversion emissions. With the increase of temperature, the green upconversion of Er3+ shows a decline while the blue upconversion of Tm3+ exhibits a rapid increase, leading to a huge contrast in both intensity ratio and emission colors. The maximum relative sensitivity can reach up to 9.86% K-1 at 303 K. It is further found that introducing Ce3+ is able to improve the sensitivity and expand the thermochromic green-to-blue gamut greatly. These results show great potential in ultrasensitive lanthanide-based nanothermometry and anticounterfeiting.

Enhancing upconversion of manganese through spatial control of energy migration for multi-level anti-counterfeiting.

The upconversion of manganese (Mn2+) exhibits a green light output with a much longer lifetime than that of lanthanide ions, showing great potential in the frontier applications like information security and anti-counterfeiting. Mn2+ can be activated by energy migration upconversion. However, there exists serious quenching interactions between Mn2+ and the lanthanides at the core-shell interfacial area, which would markedly reduce the role of Tm3+ as a ladder to facilitate the up-transition and subsequently limit the upconversion of Mn2+. Here, we propose a mechanistic strategy to enhance the upconversion luminescence of Mn2+ by spatial control of energy migration among Gd sublattice through introducing an additional migratory NaGdF4 interlayer within the commonly used core-shell nanostructure. This design can not only isolate the interfacial quenching interactions between the sensitized core and luminescent shell, but also allow an efficient channel for energy transport, resulting in enhanced upconversion of Mn2+. Moreover, the relatively long lifetime of Mn2+ (around 32.861 ms) provides new possibilities to utilize the temporal characteristic for the frontier application of multi-level anti-counterfeiting through combining the time-gating technology.

Photoluminescence and Color-Tunable Properties of Na4Ca4Mg21(PO4)18:Eu2+,Tb3+/Mn2+ Phosphors for Applications in White LEDs.

Here, the crystal structure, phase analysis, site occupancy, and luminescence properties of NCMP:Eu2+,Tb3+,Mn2+ have been studied for the first time. Under 335 nm ultraviolet excitation, the NCMP:Eu2+ phosphors show narrow-band blue emission. In addition, we discuss the reason for a continuous red shift for the emission spectra of NCMP:xEu2+ by raising the x value. The efficient ET processes of Eu2+ → Tb3+ and Eu2+ → Mn2+ were investigated by the luminescence spectra and decay curves. The ET efficiencies reach 92.58% at y = 0.15 for NCMP:0.01Eu2+,yTb3+ and 99.85% at z = 0.15 for NCMP:0.01Eu2+,zMn2+ phosphors, respectively. The efficient energy transfer processes greatly improve the quantum efficiency, luminous intensity, and thermal stability. Bright green and red emissions can be realized through changing the related ratio of Eu2+, Tb3+, and Mn2+. In addition, the excellent performance of the prepared white LED lamps utilizing a 385 nm chip combined with our prepared NCMP:Eu2+,Tb3+/Mn2+ phosphors indicates that NCMP:0.01Eu2+,yTb3+ and NCMP:0.01Eu2+,zMn2+ phosphors can be potential green and red phosphors for white LEDs.

Study on the Local Structure and Luminescence Properties of a Y2Mg2Al2Si2O12:Eu3+ Red Phosphor for White-Light-Emitting Diodes.

Structure determines properties, and properties determine applications, which is an important ideology of natural sciences. For optical materials, it is vital to lucubrate the corresponding relationship between the local crystal structure and luminescence properties for their design, synthesis, and application. This work reports a newly designed Y2Mg2Al2Si2O12(YMAS):Eu3+ red phosphor, in which difunctional Eu3+ ion is used as a red-light activator and spectroscopic probe. The qualitative and quantitative studies on the relationship between the local crystal structure and the luminescence properties of YMAS:Eu3+ are performed experimentally and computationally, using the Y3Al5O12 (YAG):Eu3+ as contrast. Moreover, compared with YAG:Eu3+, the newly designed YMAS:Eu3+ has stronger luminescence, superior Commission Internationale de L'Eclairage chromaticity coordinates, a lower optimal doping concentration, and equally excellent thermal stability. The satisfactory color-rendering index of packaged white-light-emitting diodes demonstrates its potential performance as a red phosphor. Briefly, this work provides not only a new case for the study of the local crystal structure and luminescence properties but also a new possibility for the application of a red phosphor in solid-state lighting.

Ca(Mg0.8Al0.2)(Si1.8Al0.2)O6:Ce3+,Tb3+ Phosphors: Structure Control, Density-Functional Theory Calculation, and Luminescence Property for pc-wLED Application.

A modified structure Ca(Mg0.8Al0.2)(Si1.8Al0.2)O6 (denoted as CMASO) from the evolution of CaMgSi2O6 (denoted as CMSO) codoped with Ce3+ and Tb3+ ions was designed successfully by solid reaction method for application in phosphor-converted white-light-emitting diode (pc-wLED). The Rietveld refinement of these two structures verified the changes derived from the replacement of some of the Mg2+ and Si4+ ions by Al3+ ions. The band gaps were calculated by density-functional theory (DFT) calculation method to verify the change of Al3+ ions replacing further, and the diffuse reflectance spectra (DRS) proved the veracity of the calculation result. The phosphors CMASO:Ce3+ showed blue emission excited by a wider excitation wavelength from 280 nm to 370 nm. The change of structure lead to the absorbable range broaden and the emission peak shifted to longer wavelength, compared with CMSO:Ce3+, although the amount of emitting center was the same. The reason for these phenomena was discussed in detail. The codoped phosphors CMASO:Ce3+,Tb3+ exhibited different emission colors from blue to green as the concentration of Tb3+ ions increased. Combined with commercial red phosphor CaAlSiN3:Eu2+ and ultraviolet LED (UV-LED) chips, the selected appropriate samples achieved white emission. The correlated color temperature (CCT) was 6137 K and the color rendering index (Ra) was 80.5, indicating that they could act as potential phosphors for possible applications in pc-wLED.

Novel highly efficient single-component multi-peak emitting aluminosilicate phosphors co-activated with Ce3+, Tb3+ and Eu2+: luminescence properties, tunable color, and thermal properties.

A series of emission-tunable Ce3+/Tb3+/Eu2+ doped Ca2(Mg0.75Al0.25)(Si1.75Al0.25)O7 (denoted as CMAS) phosphors have been synthesized via a high temperature solid-state reaction method. The luminescence properties, color tuning, quantum yields (QYs), energy transfer of Ce3+ to Tb3+/Eu2+, thermal stability, performance of LED devices and ratiometric temperature sensing application have been systematically investigated, respectively. Importantly, through the study of thermal stability, we found that Ce3+ and Tb3+ co-doped samples were suitable for WLED applications, while Ce3+ and Eu2+ co-doped samples were suitable for temperature sensing applications. Due to the energy transfer, Ce3+/Tb3+ co-doped samples had high luminous efficiency and the quantum efficiency of more than 80% could be achieved. Their emission colors can modulate from blue to green. In addition, on the basis of the evaluation of the as-fabricated white LED lamps via selecting the corresponding phosphors, the CCT can reach 4275 K and the CRI can increase to 86.8, indicating that this series of phosphors can act as potential color-tunable phosphors for possible applications in ultraviolet light based white LEDs. Importantly, it is found that the fluorescence intensity ratio of CMAS : 5%Ce3+,0.5%Eu2+ displays linear correlation with temperature in a wide range of 253-373 K with a high sensitivity of 2.49% K-1, indicating that it could be a good candidate for ratiometric optical thermometry.